US9328394B2 - Agent and method for tanning skins and pelts - Google Patents

Agent and method for tanning skins and pelts Download PDF

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US9328394B2
US9328394B2 US12/744,183 US74418308A US9328394B2 US 9328394 B2 US9328394 B2 US 9328394B2 US 74418308 A US74418308 A US 74418308A US 9328394 B2 US9328394 B2 US 9328394B2
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tanning
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deglycosylated
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Jens Zotzel
Stefan Marx
Heinz-Peter Germann
Alla Sarafeddinov
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/10—Vegetable tanning
    • C14C3/12—Vegetable tanning using purified or modified vegetable tanning agents
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/08—Chemical tanning by organic agents
    • C14C3/10—Vegetable tanning

Definitions

  • the present invention relates to a process for the tanning of hides and skins and to agents for performing the process.
  • animal collagen which is the main component of the skin, is altered in such a way that the leather formed by the tanning exhibits resistance to heat and microorganisms, and the smoothness of the tanned hide is retained after drying.
  • combined tanning methods such as vegetable-synthetic tanning, are used.
  • the chromium tanning method has the greatest economic importance with a worldwide proportion of above 90%.
  • the hydrated chromium complexes which become embedded between the carboxy groups of glutamic acid and aspartic acid of the collagen peptide skeleton, yield a resistant and soft leather.
  • the chromium tanning agent established a rapid and economic process conduct.
  • chromium(VI) may cause allergic reactions upon contact with the human skin.
  • chromium(III) sulfates are employed in the tanning process.
  • chromium(VI) may be formed from chromium(III) by oxidation, or it may come into the tanning process through tanning agent impurities.
  • EP 1 489 135 A1 describes the use of secoiridoids, especially oleuropein, for the cross-linking of biopolymers, for example, ⁇ -lactoglobulin, casein and other biopolymers.
  • biopolymers for example, ⁇ -lactoglobulin, casein and other biopolymers.
  • application as a tanning agent for treating leather and hides is not described. It was the object of the present invention to overcome some of the disadvantages of the prior art, especially to develop an ecological tanning process that enables the preparation of high quality tanned hides and skins with reduced amounts of chemicals without causing a dark color of the hides and skins.
  • This object is achieved by a process for the tanning of hides and skins in which the hides and skins are treated with tanning agents containing deglycosylated iridoids and/or deglycosylated secoiridoids, except for genipin.
  • Iridoids are secondary plant metabolites found in a wide variety of plant families. They belong to the large group of terpenes or isoprenoids. The designation of the parent compound is derived from the ant species Iridomyrmex detectus , which produces the compound in its defensive secretion.
  • Iridoids typically serve for defense against the plant's predators. However, they also have an antimicrobial effect and offer the plant protection from microorganisms. They have an extraordinarily bitter taste.
  • the iridoids in plants are in the form of glycosides, which are typically bound to monosaccharides, for example, glucose, by O-glycosidic bonding.
  • Preferred substances from the group of deglycosylated iridoids or deglycosylated secoiridoids include, in particular, oleuropeindial and ligustrosidedial and/or ligustalosidedial, decarbomethoxyoleuropeindial and decarbomethoxyligustrosidedial as well as (4E)-4-formyl-3-(1-formyl-2-methoxy-2-oxoethyl)hex-4-enoic acid and (4E)-4-formyl-3-(2-oxoethyl)hex-4-enoic acid.
  • suitable salts for example, alkali and alkaline earth salts, may also be used.
  • the structures of the two latter mentioned compounds are as follows:
  • the compounds employed are those in which at least one aromatic, optionally substituted, benzene ring is present, such as for oleuropeindial and the corresponding derivatives.
  • they are phenol derivatives.
  • Ligustalosides are described, for example, in Hiroshi Kuwajima, Chem. Pharm. Bull. 47 (1999), 1634-1637.
  • the ligustalosidedials are obtained by cleaving the glucose from the ligustaloside.
  • Typical suitable concentrations of the tanning agents are within a range of from 0.1 to 25% by weight, preferably from 0.5 to 10% by weight. They are typically employed in aqueous solution, optionally with further auxiliary agents.
  • a pH within a range of from 1.5 to 11 may be employed, a pH of from 2 to 7 being preferred, however.
  • Suitable temperatures are within a range of from 4 to 70° C., temperatures of from 10 to 40° C. being particularly preferred.
  • the iridoids, the secoiridoids or the correspondingly deglycosylated compounds are of plant origin, especially those derived from plants of the subfamily Oleoideae, especially those obtained from olive leaves, olive waste water or pomace.
  • the corresponding iridoids and secoiridoids or their aglycons may also be prepared synthetically.
  • the cleavage of the carbohydrates is effected enzymatically.
  • Iridoids and secoiridoids or their aglycons may also be obtained by fermentation.
  • the cross-linking of the proteins of the hides and skins is supported by the addition of further auxiliary agents, for example, by the addition of proteins, peptides, protein hydrolysates, polyamines, chitosan or polylysine.
  • the process according to the invention may also be combined with mineral, vegetable and enzymatic tanning.
  • the invention also relates to a tanning solution containing from 0.1 to 25% by weight of deglycosylated iridoids, deglycosylated secoiridoids or mixtures thereof.
  • the tanning processes according to the invention show that cross-linking through hydrogen bonds occurs in addition to covalent cross-linking.
  • the covalent bonding yields not only a substantially more stable binding of the tanning agent, but also a significant improvement of the exhaustion of the tanning liquor.
  • the poor tanning agent exhaustion of the liquor with the resulting high COD (chemical oxygen demand) contents of the waste waters is an essential disadvantage of the previously known vegetable tanning.
  • the process according to the invention not only can dispense with the use of the toxic aldehyde, but it also achieves a more intensive pretanning of the hide.
  • the substances according to the invention additionally show a bulking and fiber-isolating property. This results in a reduced demand for retanning agents having bulking properties or bulking agents in further processing.
  • the tanning process can dispense with the upstream process of pickling, i.e., the use of acids with sodium chloride, in contrast to the tanning processes industrially employed in the prior art (mineral of chromium tanning, aldehyde (pre)tanning and vegetable-synthetic final tanning). Since the use of high amounts of sodium chloride is avoided, the tannery wastewater is relieved from salt load.
  • the natural vegetable tanning agent according to the invention provides the leather with a characteristic of ecological compatibility.
  • the leather obtains a clearly discernible pleasant smell felt as a typical plant smell, in contrast to the offensive smells of chromium tanning.
  • FIG. 1 Tanning of cow hide with 4(E)-4-formyl-3-(1-formyl-2-methoxy-2-oxoetheyl)hex-4-enoic acid (Example 1).
  • FIG. 2 Tanning of cow hide with genipin (Comparative Experiment).
  • the derivatives (4E)-4-formyl-3-(1-formyl-2-methoxy-2-oxoethyl)hex-4-enoic acid and (4E)-4-formyl-3-(2-oxoethyl)hex-4-enoic acid are typically formed in aqueous solution in the presence of an acidic catalyst.
  • an acidic catalyst In particular, phosphoric acid, but also sulfuric acid and hydrochloric acid, are suitable for the preparation of the derivatives from oleuropein.
  • a photo of the tanning of cow hide is shown in FIG. 1 .
  • pH values of from 0.5 to 4 temperatures of from 20 to 80° C. and incubation times of up to 48 hours are preferably employed.
  • the aqueous solution is subsequently adjusted to a pH of 4 to 8.
  • the water is removed by spray-drying. The selection of the process conditions can be effected by the skilled person in accordance with the preparation process.
  • the incubation of the delimed cow hide with genipin was effected for 23 hours at 28° C. at a pH of 6.
  • the shrinking temperature of the tanned hides was 75° C. (left-hand side, 1% genipin) and 63° C. (right-hand side, 0.5% genipin).
  • the typical dark blue color is shown in FIG. 2 .

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Cosmetics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

Process for the tanning of hides and skins, characterized in that hides and skins are treated with tanning agents containing deglycosylated iridoids and/or deglycosylated secoiridoids, excluding tanning agents containing genipin.

Description

This application is a U.S. national stage of Application No. PCT/EP2008/065954, filed Nov. 12, 2008, which is incorporated herein by reference in its entirety.
The present invention relates to a process for the tanning of hides and skins and to agents for performing the process.
In the tanning process, animal collagen, which is the main component of the skin, is altered in such a way that the leather formed by the tanning exhibits resistance to heat and microorganisms, and the smoothness of the tanned hide is retained after drying.
In essence, three tanning methods are employed today that are based on respectively different cross-linking strategies:
  • 1. Mineral tanning with metal salts (e.g., chromium, iron, aluminum, zirconium salts). The stabilization is due to the fact that metal ions are bound by the amino acid chains in the peptide skeleton of the collagen by complex formation or by ionic interactions.
  • 2. Vegetable tanning with plant extracts (e.g., mimosa, quebracho, chestnut and tara). The stabilization is mainly based on hydrogen bonds between the tanning phenols and the peptide bonds in the skeleton of the collagen.
  • 3. Synthetic tanning with reactive organic compounds (especially with aldehydes, such as glutaraldehyde, or isocyanates). The stabilization is mainly effected through covalent linking of lysine residues of the collagen.
Further, combined tanning methods, such as vegetable-synthetic tanning, are used.
The chromium tanning method has the greatest economic importance with a worldwide proportion of above 90%. The hydrated chromium complexes, which become embedded between the carboxy groups of glutamic acid and aspartic acid of the collagen peptide skeleton, yield a resistant and soft leather. In addition to the good leather quality to be reached, the chromium tanning agent established a rapid and economic process conduct.
The use of heavy metals has a number of drawbacks. For example, it is known that chromium(VI) may cause allergic reactions upon contact with the human skin. Usually, chromium(III) sulfates are employed in the tanning process. However, chromium(VI) may be formed from chromium(III) by oxidation, or it may come into the tanning process through tanning agent impurities.
Further disadvantages of a tanning loaded with chromium or heavy metals include the complicated treatment of the waste waters by a chromium recycling waste water plant, and the expensive disposal of leather scraps, such as shavings, by dumping methods or incineration.
In the American Leather Chemist Association Meeting, Paper No. 17 (2006), “Tanning potential of Genipin”, K. Ding, M. M. Taylor and E. M. Brown describe that genipin is suitable as a tanning agent, but yields a dark blue color of the leather.
EP 1 489 135 A1 describes the use of secoiridoids, especially oleuropein, for the cross-linking of biopolymers, for example, β-lactoglobulin, casein and other biopolymers. However, application as a tanning agent for treating leather and hides is not described. It was the object of the present invention to overcome some of the disadvantages of the prior art, especially to develop an ecological tanning process that enables the preparation of high quality tanned hides and skins with reduced amounts of chemicals without causing a dark color of the hides and skins.
This object is achieved by a process for the tanning of hides and skins in which the hides and skins are treated with tanning agents containing deglycosylated iridoids and/or deglycosylated secoiridoids, except for genipin.
Iridoids are secondary plant metabolites found in a wide variety of plant families. They belong to the large group of terpenes or isoprenoids. The designation of the parent compound is derived from the ant species Iridomyrmex detectus, which produces the compound in its defensive secretion.
Iridoids typically serve for defense against the plant's predators. However, they also have an antimicrobial effect and offer the plant protection from microorganisms. They have an extraordinarily bitter taste.
Typically, the iridoids in plants are in the form of glycosides, which are typically bound to monosaccharides, for example, glucose, by O-glycosidic bonding.
Cleaving yields the deglycosylated iridoids employed according to the invention.
Preferred substances from the group of deglycosylated iridoids or deglycosylated secoiridoids include, in particular, oleuropeindial and ligustrosidedial and/or ligustalosidedial, decarbomethoxyoleuropeindial and decarbomethoxyligustrosidedial as well as (4E)-4-formyl-3-(1-formyl-2-methoxy-2-oxoethyl)hex-4-enoic acid and (4E)-4-formyl-3-(2-oxoethyl)hex-4-enoic acid. Instead of the free acids, suitable salts, for example, alkali and alkaline earth salts, may also be used. The structures of the two latter mentioned compounds are as follows:
Figure US09328394-20160503-C00001
In one embodiment, the compounds employed are those in which at least one aromatic, optionally substituted, benzene ring is present, such as for oleuropeindial and the corresponding derivatives. Preferably, they are phenol derivatives.
Ligustalosides are described, for example, in Hiroshi Kuwajima, Chem. Pharm. Bull. 47 (1999), 1634-1637. The ligustalosidedials are obtained by cleaving the glucose from the ligustaloside.
Typical suitable concentrations of the tanning agents are within a range of from 0.1 to 25% by weight, preferably from 0.5 to 10% by weight. They are typically employed in aqueous solution, optionally with further auxiliary agents.
In principle, a pH within a range of from 1.5 to 11 may be employed, a pH of from 2 to 7 being preferred, however.
Suitable temperatures are within a range of from 4 to 70° C., temperatures of from 10 to 40° C. being particularly preferred.
In a particularly preferred embodiment, the iridoids, the secoiridoids or the correspondingly deglycosylated compounds (aglycons) are of plant origin, especially those derived from plants of the subfamily Oleoideae, especially those obtained from olive leaves, olive waste water or pomace. However, the corresponding iridoids and secoiridoids or their aglycons may also be prepared synthetically. Preferably, the cleavage of the carbohydrates is effected enzymatically.
Iridoids and secoiridoids or their aglycons may also be obtained by fermentation.
In one embodiment, the cross-linking of the proteins of the hides and skins is supported by the addition of further auxiliary agents, for example, by the addition of proteins, peptides, protein hydrolysates, polyamines, chitosan or polylysine.
In one embodiment, the process according to the invention may also be combined with mineral, vegetable and enzymatic tanning.
The invention also relates to a tanning solution containing from 0.1 to 25% by weight of deglycosylated iridoids, deglycosylated secoiridoids or mixtures thereof.
Surprisingly, the tanning processes according to the invention show that cross-linking through hydrogen bonds occurs in addition to covalent cross-linking.
In contrast to the usual vegetable tanning agents whose tanning performance is limited to the hydrogen bonds to the peptide skeleton of the collagen, the covalent bonding yields not only a substantially more stable binding of the tanning agent, but also a significant improvement of the exhaustion of the tanning liquor. The poor tanning agent exhaustion of the liquor with the resulting high COD (chemical oxygen demand) contents of the waste waters is an essential disadvantage of the previously known vegetable tanning.
In contrast to the reactive synthetic organic compounds, such as glutaraldehyde, the process according to the invention not only can dispense with the use of the toxic aldehyde, but it also achieves a more intensive pretanning of the hide. The substances according to the invention additionally show a bulking and fiber-isolating property. This results in a reduced demand for retanning agents having bulking properties or bulking agents in further processing.
According to the invention, the tanning process can dispense with the upstream process of pickling, i.e., the use of acids with sodium chloride, in contrast to the tanning processes industrially employed in the prior art (mineral of chromium tanning, aldehyde (pre)tanning and vegetable-synthetic final tanning). Since the use of high amounts of sodium chloride is avoided, the tannery wastewater is relieved from salt load.
The natural vegetable tanning agent according to the invention provides the leather with a characteristic of ecological compatibility. In addition, the leather obtains a clearly discernible pleasant smell felt as a typical plant smell, in contrast to the offensive smells of chromium tanning.
In the combination with the usual chromium tanning, there are also advantages. There are fields of application in which specific processing or use demands exist, so that the use of the chromium tanning agents cannot be dispensed with (e.g., in the field of shoe upperleathers). The combined use with the process according to the invention has the advantage that radical oxidation processes that may lead to release of toxic and allergenic chromium(VI) from the leather are effectively prevented.
The invention is further illustrated by the following Examples.
FIG. 1: Tanning of cow hide with 4(E)-4-formyl-3-(1-formyl-2-methoxy-2-oxoetheyl)hex-4-enoic acid (Example 1).
FIG. 2: Tanning of cow hide with genipin (Comparative Experiment).
 Example 1
The derivatives (4E)-4-formyl-3-(1-formyl-2-methoxy-2-oxoethyl)hex-4-enoic acid and (4E)-4-formyl-3-(2-oxoethyl)hex-4-enoic acid are typically formed in aqueous solution in the presence of an acidic catalyst. In particular, phosphoric acid, but also sulfuric acid and hydrochloric acid, are suitable for the preparation of the derivatives from oleuropein. A photo of the tanning of cow hide is shown in FIG. 1.
In one embodiment of the preparation process, pH values of from 0.5 to 4, temperatures of from 20 to 80° C. and incubation times of up to 48 hours are preferably employed. The aqueous solution is subsequently adjusted to a pH of 4 to 8. For preparing a powdery formulation, the water is removed by spray-drying. The selection of the process conditions can be effected by the skilled person in accordance with the preparation process.
The incubation of the delimed cow hide with 5% (4E)-4-formyl-3-(1-formyl-2-methoxy-2-oxoethyl)hex-4-enoic acid formulation, 0.1% sodium hexametaphosphate, was effected for 18 hours at 29° C. in 200 ml of water at a pH of 6. The shrinking temperature of the tanned hide was 72° C.
Comparative Experiment
The incubation of the delimed cow hide with genipin was effected for 23 hours at 28° C. at a pH of 6. The shrinking temperature of the tanned hides was 75° C. (left-hand side, 1% genipin) and 63° C. (right-hand side, 0.5% genipin).
The typical dark blue color is shown in FIG. 2.

Claims (20)

The invention claimed is:
1. A process for a tanning of hides or skins, comprising the step of pretanning hides or skins with a tanning agent comprising at least one compound selected from deglycosylated iridoids and deglycosylated secoiridoids, said tanning agent not comprising genipin.
2. The process according to claim 1, wherein said tanning agent comprises at least one compound selected from the group consisting of oleuropinedial, ligustrosidedial and ligustalosidedial.
3. The process according to claim 1, wherein said tanning agent comprises a compound selected from the group consisting of decarbomethoxyoleuropeindial and decarbomethoxyligustrosidedial.
4. The process according to claim 1, wherein said tanning agent comprises at least one compound selected from the group consisting of (4E)-4-formyl-3-(1-formyl-2-methoxy-2-oxoethyl)hex-4-enoic acid and (4E)-4-formyl-3-(2-oxoethyl)hex-4-enoic acid or salts thereof.
5. The process according to claim 1, wherein the at least one compound is present in a concentration of from 0.1 to 25% aqueous solution in the tanning agent.
6. The process according to claim 1, wherein the process is performed at a pH of from 1.5 to 11.
7. The process according to claim 1, wherein the process is performed at a temperature of from 4 to 70° C.
8. The process according to claim 1, wherein said deglycosylated iridoids and deglycosylated secoiridoids are of plant origin.
9. The process according to claim 1, wherein said deglycosylated iridoids and deglycosylated secoiridoids are obtained from olive leaves, olive waste water and pomace.
10. The process according to claim 1, wherein said deglycosylated iridoids and deglycosylated secoiridoids are prepared synthetically, enzymatically or by fermentation.
11. The process according claim 1, wherein the tanning is supported by the addition of suitable auxiliary agents.
12. The process according to claim 1, wherein the tanning is supported by the addition of proteins, peptides, protein hydrolysates, polyamines, chitosan or polylysine.
13. The process according to claim 1, wherein the process further comprises mineral, vegetable, or enzymatic tanning.
14. The process according to claim 1, wherein the hides or skins are not darkened.
15. A tanning agent comprising 0.1 to 25% by weight of a compound selected from the group consisting of oleuropeindial, ligustrosidedial and ligustalosidedial.
16. A tanning agent comprising 0.1 to 25% by weight of a compound selected from the group consisting of decarbomethoxyoleuropeindial and decarbomethoxyligustrosidedial.
17. A tanning agent comprising 0.1 to 25% by weight of a compound selected from the group consisting of (4E)-4-formyl-3-(1-formyl-2-methoxy-2-oxoethyl)hex-4-enoic acid, (4E)-4-formyl-3-(2-oxoethyl)hex-4-enoic acid and salts thereof.
18. The process of claim 1, wherein the at least one compound is present in a concentration of from 0.5% to 10% aqueous solution in the tanning agent.
19. The process of claim 1, wherein the process is performed at a pH of from 2 to 7.
20. The process of claim 1, wherein the process is performed at a temperature of from 10 to 40° C.
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EP07121380A EP2062985A1 (en) 2007-11-23 2007-11-23 Method and device for tanning hides and pelts
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PCT/EP2008/065954 WO2009065915A1 (en) 2007-11-23 2008-11-21 Agent and method for tanning skins and pelts

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IT201600081688A1 (en) 2016-08-03 2018-02-03 Tannow S R L USE OF OIL VEGETATION WATERS IN THE TANNING INDUSTRY
CN106755629B (en) * 2016-12-30 2018-09-14 广州市骏腾皮革制品有限公司 A kind of preparation method of leather retanning agent
CN107354246A (en) * 2017-08-29 2017-11-17 安徽乐踏鞋业有限公司 A kind of anti-mildew method of leather shoes
CN112755970B (en) * 2021-01-11 2023-10-03 陕西科技大学 Treatment and resource utilization method of chromium-containing tannery wastewater based on natural biomass hydrogel
EP4379067B1 (en) 2022-12-01 2026-02-11 Institut National Des Sciences Appliquées De Rouen Iridoid derivatives and their use in a tanning process
ES3039342T3 (en) 2022-12-01 2025-10-20 Institut Nat Des Sciences Appliquees De Rouen Iridoid or seco-iridoid derivatives and their use in a tanning process
DE102023100288B4 (en) 2023-01-09 2025-12-31 CARBBIND solutions GmbH Binders, methods for their production and uses of the binder
CN116656888B (en) * 2023-05-17 2024-05-14 烟台和壹博物馆有限公司 Preparation method of environment-friendly leather, tanning agent composition and application thereof

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